DE2318930A1 - DETERGENT MIXTURES CONTAINING ENZYME - Google Patents

Description

Our No. 18 6II

The Procter & Gamble Gompany Cincinnati, Ohio, V.St.A.

Detergent mixtures containing enzyme.

The present invention relates to enzyme-containing detergent mixtures. .

e
Enzymes were originally used in detergent mixtures for their stain removing properties. There are several classes of enzymes, each of which is particularly useful for removing certain types of stain. For example, proteolytic enzymes have the ability to split or destroy proteins. Thus, proteinaceous stains on fabrics washed with a detergent mixture containing proteolytic enzyme will break down to form a shape that is more easily removed from the fabric. Similarly, amylolytic enzymes have the ability to break down carbohydrate stains, so a detergent mixture containing amylolytic enzyme is most effective at cleaning carbohydrate stains.

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; 2310930

Beeping fabrics will be. This is the case on many other types of stains and enzymes that are particularly useful for removal.

Enzymes may constitute a minor part of an entire Detergenzgemisches, eg on the order of 0.05 to 5% enzyme _S O ^. On the other hand, detergent products that contain up to 60% enzyme are also possible. Soap or synthetic detergents and any builders, bleaches, and suds improvers or antifoams are incorporated into detergent compositions to form an overall cleansing mixture. Due to the fact that the various detergent most effective at "various pHs work _s, it is difficult, which is part of the Gesamtdetergenzgemisch for each component _9, to achieve optimum cleaning performance. Normality! Enough, the pH of the solution should are set to a single value, in which the total Detergenzgemisch worked best, "This, of course? foedeutet balancing the optimum performance _s obtained from each of the individual components that ausmächen the overall Detergenzgemisch ,,. * have ZoB- most granular coarse washing agent mixtures organic and / or inorganic builders «These materials give the wash water a neutral to alkaline character licat). These materials, as well as soaps and / or organic detergents, remove a variety of soils and stains from fabrics.

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Unfortunately, in many cases, detergents and builders alone do not completely stain many stains removed. Therefore, because of their excellent stain removing properties, enzymes are included in the detergent mixtures incorporated. However, all enzymes normally added do not necessarily find optimal performance at the same pH of the washing solution as it is by the alkaline builder is imparted to the wash solution instead. Hence it is necessary in a detergent mixture only to incorporate such enzymes, its effective stain removal at the pH of the detergents containing Wash solution takes place. This necessarily limits the choice of enzymes that are effective in a detergent mixture can be incorporated, resulting in limitations on the stain removal performance of detergent equipment.

It is therefore an object of the present invention to provide an enzyme-containing detergent mixture which is effective Stains removed. Another object of the present invention is to provide an enzyme containing detergent mixture that, when used in the wash cycle, allow for optimal stain removal performance of the enzyme. Another object of the present invention is to provide an enzyme-containing detergent mixture which, when used in the wash cycle, the wash solution initially imparts an alkalinity which after one adjusted to a pH value which is most favorable for the stain removal performance of the enzyme at a predetermined time. Another object of the present invention is to provide an enzyme-containing detergent mixture which, when added to a washing solution, ■ internally adjusts the pH value of the same to successive different pH values.

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These and other goals can be found in the description below.

All percentages used herein are, if not otherwise indicated, percentages by weight.

An enzyme-containing detergent mixture which is suitable for successively different in an aqueous solution Giving pH values essentially consists of

a) a detergent such as a water soluble anionic; non-ionic, amphoteric or zwitterionic Detergent or mixtures thereof,

b) from about 0. CXDi to 10 % of an enzyme ₉ which is surrounded by a normally solid, water-soluble or water-dispersible material, which allows the enzyme to be released into the aqueous solution in a time of 0.5 minutes to 1 hour after the detergent Solution was added, allowed. And

c) a pH regulating agent in an amount, which is sufficient for the pH of the aqueous solution Change value at which the most effective use of the enzyme that takes place with one normally solid, water-soluble or water-dispersible material is enveloped, so that the agent immediately before or simultaneously with the release of the enzyme is released into the solution.

The present invention relates to enzyme-containing detergent mixtures., in particular a detergent mixture containing an enzyme with a timed release of the enzyme »

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Detergent-The mixtures according to the invention comprise enzymes and organic detergents such as water-soluble anionic, nonionic, amphoteric or zwitterionic detergents or mixtures thereof. The formulation may also contain other detergent components for various purposes. For example, for the purpose of precipitation to make the hardness conditional ions from the wash water and the detergent effectively _s organic and / or inorganic builders can be incorporated "Examples of such compounds are hereinafter referred to" bleaching agents such as chlorine or oxygen discloses compounds resulting ₃ can detergent packages according to the invention Components added to conventional detergent mixtures, such as perfume _3, colorants and the like, are also added.

The enzyme-containing detergent mixtures according to the invention may be in any physical form are present, for example as liquid or powdered _s granulated. Of particular importance are the detergents containing builders, granular enzyme-containing detergents, "which are particularly desired for cleaning coarse laundry"

Regardless of the form of the enzyme-containing detergent mixtures _9, which can be liquid or solid, the mixture, when added to the washing water ₉ , gives it a certain pH value. This pH is normally regulated by the addition of an acid or a base to the detergent mixture so that the pH is at a value at which the detergent is most effective. According to the invention, a coated enzyme and a coated pH-regulating agent are also added to the detergent mixture. The enzyme and the pH

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regulating agents are encased in a material designed to isolate these agents from the wash solution for a predetermined period of time. During this time, the basic detergent mixture performs its cleaning performance at its optimal pH condition. Thereafter, the coating of the core material regulating the pH value is dissolved or dispersed, whereby the core material located inside is released Masch solution "the pH Wert'j at which the washing solution ifflrd set ₉ = depends on the value of _s in which the added Ensyin most effectively operates. After this pH adjustment was carried out for ₅ or simultaneously therewith _s is the enzyme surrounding coating dissolved or dispergxert ₅ wherein the enzyme material to freigesetzt.wird _s at a pH on the ■ present on the tissue Fle.cken act ", which is serviceable for the stain removal characteristics of the particular Enzyms.am".

It is desired. to change the pH of the washing solution iron 0 ₅ 5 minutes to 5 minutes, preferably 2 minutes to 5 minutes after the detergent mixture has been added to the washing solution. For a Detergenzgemisch by soaking (pre-soak.) ~ Type ₉ The time ₅₁ is, wherein a pH> Modified gextfünscht _s is 30 minutes to ¹ H Stundenj, preferably from 1 hour to 3 hours "This allows .Zeitraum the basic Detergenzformulier.ung sufficient time _s exert their cleaning performance. The pH regulating agent and the enzyme are then released into the washing solution.

The enzyme that is used in connection with the present invention Can be used - includes a variety of.

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Enzymes normally applicable to detergent mixtures' are.

For the use according to the invention, alkaline proteases are particularly preferred enzymes. Alkaline proteases that are particularly suitable include subtilisin, BPN ', elastase, keratinase, carboxypeptidase, aminopeptidase, Aspergillopeptxdase A and Aspergillopeptxdase B. Subtilisin and BPN ¹ are particularly preferred. Alkaline proteases are particularly preferred. They show optimal activity in the pH range from 7.5 to 10.5.

The neutral proteases, which are also according to the invention Can be used include collagenase, chymotrypsin and trypsin and those proteolytic enzymes made from Streptomyces species can be isolated. Both chymotrypsin and trypsin show optimal activity in the neutral to alkaline range, i.e. pH 7.0 to 9.0.

Examples of acidic proteases useful in the present invention include pepsin, papain, and bromeline. Both papain and bromelin show optimal activity in the acidic to. neutral range, i.e. pH 3.0 to 7 ₉ O.

The α-amylases also form part of the present invention. All of the c-amylases show optimal activity in the acidic to slightly basic range, ie from pH 5.0 to 8.0. The α-amylases are particularly well suited for splitting starch molecules, since they are Cl ₁ ι, -glycosidic

^x i ^H / attack shorter bonds in strength »The remaining chains are easily removed from their surroundings with water or aqueous solutions of detergents. The © amylases v <ground from animal sources _{s s} cereal grains bacterial

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Sources or fungi preserved.

Other enzymes can also be used. In U.S. Patent 3,519,570, incorporated herein by reference, enzymes described, which can be used according to the invention. The pH, at which these other enzymes are most effective from the standpoint of detergent stain removal, can be determined through experimentation.

Commercially available enzymes are generally in the form of dry powders consisting of about $ 2 to about $ 80 active enzyme in combination with a powdery powder inert vehicles such as sodium or calcium sulfate or sodium chloride as the remainder in an amount of $ 20 to $ 98, available. The one used in the present description

'I-

The expression "enzyme" means the active enzyme in combination with the inert vehicle.

The term "pH regulating agent" as used in ' Used in connection with the present invention includes those acids and bases which, when an aqueous Solution added are able to adjust the pH. to change the same.

The special, pH-regulating agent whose .. Quantity, the material used for the wrapping and the thickness of the enveloping material are all of the basic detergent formulation and the enzyme to be incorporated therein.

coating materials used to coat the pH controlling agent and enzyme are used,

must be water-soluble or water-dispersible. Any suitable material can be used as a coating agent, e.g. higher fatty alcohols, preferably those with 12 to 18 carbon atoms (e.g. laury alcohol, coconut fatty alcohol, cetyl alcohol, steary alcohol), mineral oil, the higher fatty acid amide compounds, preferably those with 12 to 18 carbon atoms in the acyl radical (primary amides and the corresponding monoethane amides, isopropanolamides and diethanolamides of lauric acid and coconut acid and myristylic acid) and their ethylene oxide reaction products with up to about 5 moles of ethylene oxide, the higher fatty acids, preferably those with 12 to 18 carbon atoms, such as stearic acid, palmitic acid, Tallow fatty acids and the like. Other coating materials are the wax-like polymers of ethyl glycol such as "Carbowax 1500", "2025" and 4000 ", the soluble starches and dextrins and the like. These materials can have very limited solubility in water to extreme water solubility, but are retarded effective the solubility or. Fr Their core or their internal material is immersed in the cleaning solution. The term "water-dispersible coating agent" or equivalents as used herein refer to agents of varying water solubility or dispersibility but which become dispersed or dissolved under the conditions of use of the product. For example, organic materials such as lauryl alcohol and lauryl acid amides and alkylolamides have limited water solubility but tend to dissolve into the cleaning solution in the presence of organic detergent material. Any suitable manner may be used; be, to apply the coating agent to the particles of the. Apply ρH-fourth regulating agent. It is preferred that _s the coating agent dissolved, suspended or dispersed in a suitable solvent

3 0 S 8 4 4/1 0 5 4

or heated to a molten shape and then used for Education of the desired! Coating can be sprayed or finely atomized onto the individual acid particles. Each suitable solvents can be employed, e.g., a normally gaseous propellant all in one. Pressure vessel, Examples are the normally gaseous hydrocarbon and carbonated hydrocarbon propellants low molecular weight such as propane, butane, halogenated ethanes and methanes. The propellants, known as "Freons" and "Genetrans", e.g., dichlorodifluoromethane and monochlorodxfluorathane are suitable. Other solvents or dispersing agents can also be used suitably Media such as ethanol, isopropanol and aqueous alcoholic mixtures are used. In this way and Way can be a complete coating or film on the surface of the particles of the pH regulating agent Be obtained by means of. If the coating agent is normally solid, it will dry into a film and if so it is usually liquid, it gets on the surfaces the particle adsorbs or absorbs. The coating material can be prepared by mixing the coating agent in powder form with the particles of the pH control agent using suitable mechanical devices Mixing, including throwing back and forth in one Rotary drum, also in solid form, on the surfaces the particles of the pH regulating agent are applied.

The pH regulating agent constituting the core material is preferably normally solid. Optionally can be a normally liquid material by suitable combination with a solid carrier in finely divided form ^ how diatomaceous earth or bentonite are used »Examples for suitable acid »are the organic acids

447 10 Si

such as tartaric acid, maleic acid, boric acid, and glutamic acid their lactone. Suitable inorganic acids and acid salts such as sulfamic acid and phosphoric acid and sodium bisulfate can also be used. Examples of suitable basic materials are the alkali metal hydroxides, e.g. Sodium and potassium hydroxide, as well as alkali metal carbonates, phosphates, silicates and oxides and ammonium compounds.

The enveloping of the enzyme is also done around the Postpone the time at which the enzyme is exposed to the washing solution. The special wrapping material and its thickness is chosen to facilitate the release of the enzyme into the washing solution simultaneously with or immediately ■ after releasing the acidic or basic material. The particular, above with regard to the coating material for the acidic or basic compound given are examples of the coating materials Materials that are also suitable for encasing the enzyme. By suitable choice of the coating material and / or its thickness, the release of the enzyme into the washing solution is regulated at the same time as or immediately after (on the order of 1 second to 10 seconds) the release of the acidic or basic compound he follows.

In a preferred embodiment of the present In the invention, the enzyme and the pH-regulating agent form a unit consisting of individual parts (discreet unit). This means that the enzyme forms the core and has a water-soluble or water-dispersible coating. This Coating has a coating of a pH regulating agent Agent, which in turn has a second water-soluble or water-dispersible coating.

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-Vl-

Therefore, when this agent is added to the washing solution, this second coating delays the point in time at which the pH-regulating agent of the washing solution is set to a predetermined period of time. Thereafter, the pH-regulating agent is released, which in turn exposes the inner water-soluble or water-dispersible coating to the washing solution. This one will eventually also detached, releasing the enzyme. This preferred embodiment ensures that the enzyme is released at the appropriate pH condition, since the outer coating consists of a pH regulating agent Fund must first be released.

A preferred enzyme-containing detergent mixture is essentially from

a) a water-soluble alkaline build-up,

b) an anionic, non-ionic, amphoteric or zwitterionic detergent or mixtures thereof as detergent in a ratio of detergent to builder from 10: 1 to 1:10,

c) from 0.05 % to 5 % of a proteolytic enzyme that exhibits optimum stain removal performance at pH 7 to 9 and is coated with a sufficient amount of a water soluble or water dispersible material that the enzyme concurrently with or immediately after the Release of the pH

"regulating agent released by d), and

d) a sufficient amount of a pH regulating agent

Means that with a water-soluble or water-dis-

is
pergeable coating envelops / f around the pH value of the washing

solution to adjust from 7 to 9, the enveloping 309844/1054

Material releasing the pH regulating Mean up to 0.5 minutes to 5 minutes after the Detergent mixture was added to the wash solution for the first time.

The above-mentioned detergent mixture x is used as a Coarse detergent mixture containing builders, the is suitable for washing soiled fabrics. The following sequence of stages takes place when the above Detergent mixture is added to the wash water:

1) The detergent and builder go into solution (where the washing water is given a pH value of 9 »5 to 10.5) and act on the laundry for up to 5 minutes,

2) after 0.5 to 5 minutes the pH regulating agent is released, the pH of the washing solution increasing a value from 7 to 9 is changed,

3) the coating surrounding the proteolytic enzyme becomes at the same time / baer immediately after the release of the dissolved or dispersed the pH regulating agent, wherein the enzyme is released into a wash solution of pH 7 to 9, a pH at which the stain removal property of the enzyme can be unfolded most favorably.

Examples of soaps and synthetic anionic, nonionic, amphoteric or zwitterionic detergents are:

A. Anionic soap and non-soap synthetic detergents

This class of detergents includes common alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids with from about 8 to

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- 14 - ■■ '; ;

24 carbon atoms and preferably with about 10. up to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources such as vegetable and animal esters (eg palm oil, coconut oil, babassu oil, soybean oil, castor oil, TaIgOl ₃ male and fish oils, fat, lard and mixtures thereof). The fatty acids can also be produced synthetically (for example by oxidation of petroleum or by hydrogenation of carbon monoxide according to the Fish ^ Tropseh process). Resin acids such as rosin and the resin acids in tall oil are suitable. Naphthenic acids are also suitable. Sodium and potassium soaps can be obtained by direct saponification of fats and oils or by neutralizing free fatty acids, which are produced in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, ie, sodium or potassium tallow and coconut soaps. ,

This class of detergents also includes water-soluble ones Salts, especially the alkali metal salts of organic ones sulfuric acid reaction products »which have an alkyl radical in their molecular structure with from about 8 to about 22 carbon atoms and a residue of a sulfonic acid or a sulfuric acid ester. (The term alkyl includes the alkyl portion of higher acyl groups). Examples this group of synthetic detergents which contain some of the builder-containing substances preferred according to the invention Forming detergent mixtures are the sodium or potassium alky! Sulfates, in particular those that are through Sulphation of higher alcohols (Cg - C.g carbon atoms obtained by reducing the glycerides of tallow or coconut oil, are produced, sodium

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or potassium alkylbenzenesulfonates, in straight or branched figs chain configuration, wherein the alkyl group contains from about to about 15 carbon atoms, e.g., those of the in U.S. Patents 2,220,099 and 2,477,383 Type (linear straight-chain alkylbenzenesulfonates are particularly valuable, where the average of the alkyl ^ groups contains about 13 carbon atoms and the following as C .-, LAS), sodium alkyl glyceryl ether sulfonate, especially the ethers of higher alcohols derived from tallow and coconut oils, Sodium Coconut Oil Fatty Acid Monoglyceride Sulfonate and sulfates, sodium or potassium salts of sulfuric acid esters of the reaction product of: 1 mole of a higher Fatty alcohol (e.g. tallow or coconut oil - alcohols) and about 1 to 6 moles of ethylene oxide, sodium or potassium salts of alkylphenolethylene oxide ether sulfate with about 1 to about

Ethylene oxide units per molecule, the alkyl radicals from about 8 to contain about 12 carbon atoms.

Phosphap anionic surfactants are also useful in the present invention. These compounds are surface-active materials with substantial cleaning properties that bind the hydrophobic moieties together, an oxyacid of phosphorus. The more common solubilizing groups are naturally-SO ^ H, -SO ₃ H and -CO ₂ H. Alkyl phosphate esters such as (RO) ₂ PO ₂ H and ROPO ₂ H, in which the radical R is an alkyl chain having about 8 to 20 carbon atoms, are also useful. These esters can be modified by inserting 1 to about 40 alkylene oxide units, for example ethylene oxide units, into the molecule. Are formulas for these modified anionic phosphate detergents

+) in which the anionic solubilizing group,

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ir

P-O-M

[RO- (CH ₂ CH ₂ O) _n 1 POM

0-M

where R is an alkyl group having from about 8 to 20 carbon atoms or an alkylphenyl group in which the alkyl group contains from about 8 to 20 carbon atoms, .and M a soluble cation such as hydrogen, sodium, potassium, ammonium or substituted ammonium and η a number of 1 to about 40.

Another class of suitable anionic organic Detergents which are particularly useful according to the invention, include salts of 2-acyloxyalkane-1-sulfonic acids «these Salts have the formula

• o · ■■■ .- '..

OCR ₀ . '

! ^£
., R -.CH - CH ₂ SO ₃ M "

wherein FL is an alkyl radical of from about 9 to about 23 carbon atoms (which form an alkane radical with the two carbon atoms), R "is an alkyl radical with 1 to about -8 Carbon atoms and M a salt-forming radical. ,

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The salt-forming radical M in the structural formula given above is a water-solubilizing cation and can e.g. an alkali metal cation (e.g. sodium, potassium, lithium), an ammonium or a substituted ammonium cation be. Specific examples of substituted ammonium cations include methyl, dimethyl and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those that are derived from alkylamines, such as ethylamine, diethylamine, Triethylamine, mixtures thereof and the like are derived.

Specific examples of .beta.-acyloxy-alkane-1-sulfonates, or alternatively 2-acyloxy-alkane-l-sulfonates, the present invention superior to provide cleaning performance under substantially neutral wash conditions are useful, the sodium salt comprise from 2-acetoxy-tridecanl-sulfonic _s the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid, the lithium salt of 2-butanoyloxytetradecane * -! - sulfonic acids the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid, the sodium salt of 2-acetoxy-hexadecane-1- sulfonic acid, the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid, the sodium salt of 2-acetoxyheptadecane-1-sulfonic acid, the lithium salt of 2-acetoxyoctadecane-1-sulfonic acid, the potassium salt of 2-acetoxynonadecane-1-sulfonic acid of 2-acetoxyuncosane-1-sulfonic acid, the sodium salt of 2-propionyloxydocosane-1-sulfonic acid and its isomers.

Preferred β-acyloxy-alkane-1-sulfonate salts are the alkali metal salts von.ß-acetoxy-alkane-1-sulfonic acids of the above named formula, wherein R ^ is an alkyl radical having about 12 to about 16 carbon atoms, where

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- 18 -:. ■: ■. ■

these salts from the point of view of their excellent cleaning properties and their ready availability are preferred.

Typical examples of the β-acetoxyalkanesulfonates described above are described in the literature. Belgian patent specification 65O 323 discloses the manufacture of certain 2-acyloxy alkanesulfonic acids. Reveal similarly U.S. Patents 2,094,451 and 2,086,215 certain salts of ß-acetoxy-akanesulfonic acids. The present is based on this Patent references are referenced.

A preferred class of anionic organic detergents are the ß-alkyloxy-alkane sulfonates. These compounds have the following formula.

OR ₂ H

J I

H * H

SO ₃ M

where R "is a straight-chain alkyl radical having from 6 to 20 carbon atoms, R _{? is} a lower alkyl radical having from 1 to 3 carbon atoms and M is a salt-forming radical, as described above.

Specific examples of ß-alkyloxy-alkane-sulfonates or alternatively 2-alkyloxy-alkane-l-sulfonates, which are to be provided superior cleaning and whiteness grades are suitable under household washing conditions, include -

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Potassium ß-metoxydecanesulfonate,
Potassium-ß-metoxy-trideeansulfonate _s
Potassium ß-ethoxytetradecylsulfonate, sodium ß-isopropoxyhexadecylsulfonate, lithium ß-tertbutoxytetradecylsulfonate, sodium ß-metiOxyoctadepylsulfonat and ammonium-ß-n-propoxydodecylsulfonat.

Other synthetic inorganic detergents useful in the present invention are alkyl ether sulfates. These materials have the formula RO (C ₂ H ₂₁ O) _x SO ₅ M wherein R is an alkyl group or an alkenyl group of about Io to about 20 carbon atoms, χ llbis 30 and M a, processin ^ eS meanings as above ₇ salt-forming cation.

The alkyl ether sulfates used in accordance with the invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably R Ik has up to 18 carbon atoms. The alcohols can be derived from fats, for example coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from tallow are preferred. Such alcohols are reacted with 1 to 30 and preferably 6 molar proportions of ethylene oxide and the resulting mixture with, for example, an average of 6 Molen.ätthylenoxid per mole of alcohol is sulfated and neutralized.

Specific examples of the alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulphate, lithium tallow alkyl triethylene glycol ether sulphate and sodium tallow alkyl hexaoxyethylene sulphate.

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Due to their excellent cleaning properties and easy availability, the alkali metal coconut and -tallow-alkyloxyethylene ether sulfate with an average from 1 to about 10 oxyethylene units are preferred. The alkyl ether sulfates to be used according to the invention are known compounds and are in US-PS 3,332,876, referred to is described.

Further examples of non-soap anionic synthetic detergents falling within the scope of the present invention are the reaction product of fatty acids esterified with isethionic acid and with sodium hydroxide are neutralized, e.g. if the fatty acids are derived from coconut oil, sodium or potassium salts of fatty acid amide of methyl tauride, in which the fatty acids are derived, for example, from coconut oil. Other anionic synthetic detergents are disclosed in U.S. Patents 2,486-921, 2,486,922 and 2,396,278.

More examples of anionic, non-soap synthetic Detergents falling within the scope of the present invention fall are the compounds that contain two anionic functional groups. These are called di-anionic Called detergents. Suitable di-anionic detergents are the disulfonates, disulfates or mixtures same of the general formulas

R (.SO ₃ ) ₂ M ₂ , .- ■ .- R (SO ₄ J ₂ M ₂ , R (SO ₃ ) (SO ₄ ) M ₂

where R is an acyclic aliphatic hydrocarbyl radical having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example the C ₁₁ - - Cp _Q -dinatrium

3 0 98-4 / 1054

1,2-alkyl disulfates, CLj- - Cp ₀ -dicalum-l, 2-alkyl disulfonates or disulfates, disodium-l ^ -hexadecyl disulfate, C ^^ to Cp ₀ -disodium-1,2, 2-alkyl disulfonate _a disodium-l, 9 -stearyl disulfates and 6,10-octadecyl disulfates. . .

The aliphatic fraction of the disulfates or disulfonates is generally essentially linear, due to the fact that it is the detergent compound, among other reasons imparts desirable biodegradable properties is desirable. The water-solubilizing Cations include those customarily known in detergent technology Cations, i.e. the alkali metals and the alkaline earth metals, as well as other metals of the groups HA, HB, IHA, IVA and IVB of the Periodic Table of the Elements, excluding Boron »The preferred water-solubilizing agents Cations are sodium and potassium cations. These dianionis see Detergents are described in British Patent 1-151,392.

Other anionic synthetic detergents include those as Suceinamate designated class, This class includes such surfactants, as disodium N-octadecylsulfosuccinamate, Tetrasodium-N-Cl ^ .- dicarboxyäthyD-N-octadeeyi-sulfo-succinamate, Di ^ amyl ester of sodium sulfosuccinic acid, Dihexy! Ester of sodium sulfosuccinic acid, dioetyl ester of sodium sulfosuccinic acid.

Other suitable anionic ones which can be used in accordance with the invention Detergents are olefin sulfates with from about 12 to about 24 carbon atoms. The term "olefin sulfonates" is applied in the present case to connections that are carried out by Sulphonation of arOlefin with non-complex-bound

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Sulfur trioxide and subsequent neutralization of the acidic reaction mixture under such conditions that each suit on. Which was formed during the reaction is hydrolyzed to form the corresponding hydroxyalkanesulfonates. The sulfur trioxide can be liquid or gaseous and is usually, but not necessarily, when used in liquid form, by inert diluents, e.g. by liquid SO, chlorinated hydrocarbons, etc., or when used in gaseous form, by air , Nitrogen, gaseous SO ₂ and the like. Diluted.

The α-olefins from which the olefin sulfonates are made are derived from mono-olefins having 12 to 2k carbon atoms, preferably 14 to 16 carbon atoms. They are preferably straight chain olefins. Examples of suitable 1-olefins are 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-tetra- coses.

In addition to the actual alkene sulfonates and a proportion of hydroxy alkanesulfonates, the contain Olefinsulfonate, depending on the reaction conditions, the proportions of the respondents, the Nature of the starting olefins and the impurity in that Stock olefin and side reactions during the sulfonation reaction, smaller amounts of other materials, such as alkene, disulfonate.

A specific anionic detergent used for the present invention is particularly suitable in U.S. Patent 3,332,880, incorporated herein by reference. "

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B. Nonionic Synthetic Detergents.

synthetic
Nonionics / detergents are broadly defined as compounds that are produced by condensation; of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene moiety condensed with each individual hydrophobic group can be easily adjusted to achieve a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements.

For example, a well-known class of non-ionic detergents are commercially available under the name Pluronic. These convolutions are caused by condensation and of Ethylene oxide and a hydrophobic base obtained by condensing propylene oxide with propylene glycol, manufactured. The hydrophobic part of the molecule, which is naturally insoluble in water, has a Molecular weight from about 1,500 to 1,800. The addition of polyoxyethylene residues to this hydrophobic part tends tends to increase the water solubility of the molecule as a whole, and the liquid character of the product will Maintained to the point where the polyoxyethylene content about 50% of the total weight of the condensation product matters.

Other suitable non-ionic synthetic detergents include:

1) The polyethylene oxide condensates of alkylphenols, e.g. the condensation products of alkylphenols with a either straight or branched chain alkyl group, the

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Contains from about 6 to 12 carbon atoms, with.
Ethylene oxide, the ethylene oxide being available in amounts of 5 to moles of ethylene oxide per mole of alkylphenol. Of the
Alkyl substituents of such compounds can be, for example, from
polymerized propylene _s diisobutylene, octene or honing.

2) compounds which are derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and _o Äthyldiamin product. ZB'verbindungen from about 40 to about 80 wt -.% Polyoxyethylene groups and having a molecular weight of about 5,000 to about Hoooo, and 'groups in the reaction of "> Äthylenoxid- with a hydrophobic base obtained from the reaction product of ethylenediamine and excess ethylene oxide is obtained, the base having a molecular weight in the order of magnitude of 2,500 and 3–00 °, -are- satisfactory ο

3) The condensation product of aliphatic alcohols with

either

from 8 to 22 carbon atoms in "straight or branched chain configuration j, with ethylene oxide _s for example a coconut alcohol-ethylene oxide condensate with from 5 to 30
Moles of Äthyl.enoxid per mole of coconut alcohol _s where the
Coconut alcohol fraction has from 10 to 14 carbon atoms. ·.

4) Nonionic detergents include nonylphenol, the with either about 10 or about 30 moles of ethylene oxide per Mole of phenol is condensed «, and the condensation products of coconut alcohol with an average of either about 5-5 or about 15 moles of ethylene oxide per mole of alcohol

9844 / 1OS 4

and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.

Other examples include dodecyl phenol, the one with 12 moles Ethylene oxide is condensed per mole of phenol, Dinony! Phenol, which is condensed with 15 moles of ethylene oxide per mole of phenol, dodecyl mercaptan with 10 moles of ethylene oxide per Molar of mercaptan is condensed, bis- (N-2-hydroxyethyl) -lauramide, nonylphenol, which with 20 moles of ethylene oxide per Mole of nonylphenol is condensed, myristyl alcohol, which condenses with 10 moles of ethylene oxide per mole of myristyl alcohol is, lauramide, containing 15 moles of ethylene oxide per mole of lauramide is condensed and di-isoocty! phenol, which has 15 moles Ethylene oxide is condensed.

5) A detergent of the formula RR Er-Kf -—> 0 (amine oxide detergent), wherein R is an alkyl radical having from about 10 to about carbon atoms, from 0 to about 2 hydroxyl groups and from 0 to about 5 ether bonds _s where at least one unit R ^x is present, which is an alkyl group with from about 10 to about 18 carbon atoms * and 0 ether bonds, and R and R ^ each represent alkyl radicals or hydroxyl radicals with from t to about 3 carbon atoms.

Specific examples of amine oxide detergents are dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylarainoxide, dimethylstearylaminojsio, cetylethylpropylarainoxide, diethyldodecyl-. amine oxides Diäthyltetradecylarainoxid "Di ^ propyldodecylaminoxid _s bis- (2-hydroxyethyl) dodecylamine oxide _i) ethyl) _{r3-dodecoxy-l-s} hydroxypropylaminoxid propyl) methyltetradecylaminoxid _s Dimethyloleylaminoxid _a dimethyl-C2-hydroxydodecyl) aainoxiö and the corresponding

309844/1064

Decyl, hexadecyl and octadecyl homologues of the above compounds. ^

12 3

6) A detergent of the formula RRR ^ p > O (phosphine oxide-

Detergent) wherein R is an alkyl group having from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 fitherb to about 5 indungen, wherein at least one unit R is present _s which an alkyl group having from about 10 to about 18 carbon atoms, and 0 ether bonds

2 ~ * i
and R and R each represent alkyl radicals or hydroxyalkyl radicals having from 1 to about 3 carbon atoms.

Specific examples of phosphine oxide detergents are Dimethyldodecylphosphinoxidü, whore thyltetradecylphosphinoxid, Äthylmethyltetradecylphosphinoxid, Cetyldimethylphosphinoxidj Dimethylstearylphosphinoxid, Cetyläthylpropylphosphinoxid, Diäthyldodecylphosphinoxid, Diäthyltetradecy! Phosphine oxides Dipropyldodecylphosphinoxid _s "Up-ChydroxymethyD-dedecylphesphinoxids bis (2-hydroxyäthyD-dodecylphosphine oxide, (2 ^ hydroxypropyl) -methyltetradecylphosphinoxid, Dimethyloleylphosphinoxid and dimethyl-2-hydroxydodecyl) phosphine oxide and the corresponding decyl "hexadecyl and octadecyl homologues of the above compounds",

7) A detergent of the formula

1 ■. ■■ '
RS-

1 - - ■

(Sulfoxide detergent), wherein R is an -alkyl radical- having from about 10 to about 28 carbon atoms _s of. 0 "to about 5

309844/1054

Ether bonds and from 0 to about 2 hydroxyl substituents, where at least one radical R is an alkyl radical with O ether bonds and is from about 10 to about 18 carbon atoms, and wherein R is an alkyl radical having from 1 to 3 Mean carbon atoms and from 1 to 2 hydroxyl groups, e.g. octadecylmethylsulfoxide, dodecylmethylsulfoxide ,. Tetradecylmethyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 3-methoxytridecylmethylsulfoxide, 3-hydroxy-4-dodecoxybutylmethylsulfoxldj Octadecyl-2-hydroxyethyl sulfoxide, Dodecylethyl sulfoxide. "'

C Ampholytic, synthetic detergents.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one has an anionic water-solubilizing group, for example carboxy, sulfo ₉ sulfato group.

Examples of compounds that fall under this definition are sodium 3- (dodecylamino) propionate, sodium 3- (dodecylamino) propane-l-sulfonate, sodium 2- (dodecylamino) ethyl sulfate, sodium 2- (dimethylamino) octadecanoate, disodium 3- (N-carboxymethyldodecylamino) propane isulfonate, disodium octadecyl iminodiacetate, sodium ί-carboxymethyl-2-undecylimidazole and sodium N _s N-bis (2-, hydroxyethyl) -2-sulfato-3 -dodecoxypropylamine.

309844/1054

D. ■ Zwitterionic Synthetic Detergents.

Zwitterionic synthetic detergents can be described as derivatives of aliphatic quaternary ammonium and phosphonium 'or tertiary sulfonium compounds in which the cationic radical can be part of a heterocyclic ring and in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 3 to 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water-solubilizing group, for example carboxy, sulfo, sulfato, phosphato or phosphono group. Examples of compounds which fall within this definition are 3- _s (NJN-dimethyl-N-hexadecylammonio) -2-hydroxypropane-lsulfonat, 34 (N, N-dimethyl-N-hexadecylammonio) propane-lsulfonat, 2- (N, N-dimethyl-N-dodecylammonio) acetate, 3- (M, N-dimethyl-N-dodecylammonio) propionate, 2- (N, N-dimethyl-N-octadecylammonio) ethyl sulfate, 2- (trimethylammonio ) Ethyl dodecylphosphonate, ethyl 3- (N, N-dimethyl-N-dodecylammonio) propylphosphonate, 3- (P, P-dimethyl-P-dodecylphosphonio) propane-1-sulfonate, 2- (S-methyl-S -tert.-hexadecylsulfonio) -ethane-1-sulfonate, 3- (S-methyl-S-dodecylsulfonio) propionate, sodium 2- (N3N-dimethyl-N-dodecylammonio) "-ethylphosphonate, 4- (S-methyl -S-tetradecylsulfonio) -butyrate,! - (^ - HydroxyäthylJ ^ -undecylimidazolium-1-acetate, g-C-trimethylammonioJ-octadecanoate and 3- (N ₉ N-Bis ™ (2-hydroxyethyl) -N-octadecylammonio) -2- hydroxypropane sulfonate Some of these detergents are described in U.S. Patents 2,129,264, 2,178,353, 2,17H, 786, 2,813,898, and 2,828.

Builders which are suitable for use in the detergent mixtures according to the invention containing builders, ^{sinafoleen <äe:} 3098U / 105 «

Examples of suitable water-soluble, inorganic alkaline detergent builder salts are alkali metal carbonates, -borates, -phosphates, -polyphosphates, -bicarbonates, -silicates and -sulphates. Specific examples of such Salts are sodium and potassium tetraborates, perborates, bicarbonates, carbonates, triphosphates, pyrophosphates, orthophosphates and hexametaphosphates. Sodium sulfate, although not an alkaline builder salt classified is included in this category.

Examples of suitable organic alkaline detergent builder salts are 1) water-soluble aminopoly carboxy late, for example sodium and potassium ethylene-dj-amine tetraacetate, nitrilotriacetate.and -N (2-hydroxyethyl) nitrilodiacetate, 2) water-soluble salts of phytic acid, _see eg sodium and potassium phytate (compare US-PS 2-739 9 ^ 2) _s 3) water-soluble polyphosphonates, especially sodium _s. Potassium and lithium salts of ethane-1-hydroxy-l ^ l-diphosphonic acid, sodium - _£ potassium and lithium salts of methylenediphosphonic acid, sodium - potassium and lithium salts of ethylenediphosphonic acid and sodium _s potassium and lithium salts of ethane-1,2,2-triphosphonic acid «. Other examples include the alkali metal salts of Sthan-S-carboxy-isl-diphosphonsäureg Hydroxymethandiphosphonsäurej, Carbonyldiphosphonsaure ^ ethane-l-hyäroxy-l 'l _{s 2-ethane-2-fl} triphosphoneäure hydro3iy-I _{3 s} 1,2-triphosphonic propane i "1 _S 3 _S 3 ~ t" etraphosphonsäure _s propan-lsljS'sS-tetraphosphonic acid and Βνορ & η · Ί _ΰ 2 _ΰ 2 _ΰ 3 ~ tetraphosphonic _a H) water-soluble salse of Polycarbosssrlatpolymeren and copolymers _a as described in US-P5 3308 Όβ7 are described ^ especially a detergent builder material which consists of a water-soluble salt of a polymeric aliphatic polycarboxylic acid ₃ the

209844 /

as to the position of the carboxylate groups, the following has structural relationships and has the following prescribed physical properties:

a) a minimum molecular weight of about 350 in the Acid form,

b) an equivalent weight of about 50 to about 80 in the Acid form,

c) have at least 45 moles of the monomeric species 2 carboxyl radicals separated from each other by no more than 2 carbon atoms are separated,

d) the point of attachment of the polymer chain of each carboxyl-containing radical is separated from the point of attachment of the next carboxyl-containing radical by no more than 3 carbon atoms along the polymer chain. Specific examples include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic _s fumaric acid, methylenemalonic acid and citraconic acid and copolymers with the same and other acceptable monomers, such as ethylene, and 5) mixtures thereof.

Mixtures of organic and / or inorganic builders can be used and are generally desirable. Such a mixture of scaffolding taffes is. described in U.S. Patent No. 3,392,121., for example, ternary mixtures of sodium tripoylphosphat _s sodium nitrilotr.iacetat and Trinat'Tium-ethylene-l-hydroxy-lal-diphosphonate. The builders described above can also be used individually according to the invention.

In addition, other builders such as water-soluble salts of Mellitsäurej, citric acid can _see pyromellitic acid, benzene penta carboxylic acid _s oxydiacetic and oxydisuccinic be used satisfactorily "

309844/1054

The builder-containing detergent mixtures of the present invention contain a water-soluble detergent and a builder in a weight ratio of 10: 1 to 1:10. The amount of builder in the builder-containing detergent mixture is preferably from 20 to 50 % with a detergent: builder weight ratio of 2: 3 to 1: 5.

Numerous known materials can optionally be incorporated into the product. -Z. B. small amounts anti-caking agents, dirt suspending agents Agents, antiseptics, germicides, perfumes, optical brighteners, fluorescent agents, and the like. The Detergent mixtures can also contain numerous other components that are specific to the time Release encased in ax washing solution. For example, an enzyme inactivator such as an oxygen or Chlorine bleach, for release into the washing solution after the enzyme has had an opportunity to remove any stains to be removed from the soiled laundry. The wrapping material can either be enzyme-degradable or be a water soluble or dispersible coating that is appropriate (either by the specific material or by the coating thickness), the enzyme inactivator a specific point in the wash cycle. to release.

Similarly, if necessary, coated bleaching agents, cationic water softeners or anti-septic agents can be included in the detergent mixture of the present invention. These materials are used for controlled Release into the wash solution with those listed above

3Q98U / TQE4

'■ ■ - 32. -

Wrapping materials wrapped.

Bleaching agents which are suitable for the present invention are all the bleaching agent _s that are normally present in detergent formulations, such as hydrogen peroxide addition compounds, cyanurates, and the organic peracid = The organic peracid compounds are preferred. Examples of these compounds can be found in U.S. Patent 3,0-5,921. These bleaches are most effective at pH 7.0 to 9.0. Accordingly, the coating material and its thickness are chosen so as to release the bleach when the pH of the washing solution is 7.0 to 9.0. Since the bleaching agents used in the detergent mixtures are incompatible with most of the enzymes, it is necessary in connection with the present invention that the bleaching agent and the enzyme are released at different times and therefore also at different pH conditions * '

Cationic softener _s -in which at a pH · range from 3 to 7 are effectively _s mixture may be also included in the present invention ''

Soil release agents, such as copolymers of maleic anhydride and a vinyl compound, are most effective when a wash solution has a pH of 5-7. Accordingly, the coating material "are the _s .the cationic softener and the soil-containing compound _s and the thickness thereof selected such that the release takes place its core in the washing solution at the optimal pH loading conditions ·.

309844/1054

It will be understood, however, that the addition of the above optional components to the detergent mixture will require the addition of pH regulating agents containing different coating materials and / or thicknesses. In other words, it may be necessary to formulate a detergent mixture so that the following sequence of steps is carried out: (1) immediate dissolution of detergent and builder, (2) release of an agent that regulates the pH value so that the washing solution is adjusts the pH value, (3) release of the enzyme simultaneously with or immediately after the release of the acid or base in the above-mentioned step (2) _s (H) release of additional pH-adjusting agents to raise the pH value set a different value, and (5) release of other optional compounds such as the cationic _s Enthärtungsmittels ₉ soil release agent or the bleaching agent. This sequence of steps can be varied as long as each coated component contained in the detergent mixture is released under the pH conditions that are most suitable for its performance.

The following examples serve to illustrate the present Invention.

309844/1054

example 1

The following mixtures were made:

Geraisch mixture 25 % A. B. 10 % 25 % 25 % 10 % 15 % 25 % 20 % 15 pounds 20 %

Sodium carbonate sodium citrate Sodium salt of a linear alkylbenzenesulfonate Sodium silicate sodium sulfate

enveloped Monsanto DA-10 enzyme. (0.1 % enzyme and 0.1 % coating agent) '- ■■ -. 0.2

Monsanto DA-10 0.1 % -

coated sulfamic acid

(0.7 % acid and 0.3 % coating agent) - 1

Rest (water) ^, 9 % - 3.8-

The linear alkylbenzenesulfonate has an average of 12 carbon atoms in the alkyl chain, while the sodium silicate has a SiOp ¹ Na ₂ -O ratio of 2.0. Monsanto DA-10 enzyme is a proteolytic enzyme that exhibits optimal stain removal properties at pH 7.0 to 8.5. The enzyme and sulfamic acid of Mixture B were each coated with Carbowax 4,000, a normally solid polyethylene glycol with a molecular weight of about 4,000. .

Each mixture was designed for its particular stain removal properties tested, it being used for washing individual

098 4 4/1054

Cotton strips containing spinach, liqueur ₃ beef liver and sauce stains were used. The washing solutions contained water with a hardness of 6.7 ° dH and had a temperature of 51.5 ° C. Three cotton strips, each containing one of the stains listed above, were added to the wash solution. Mixture A was added to a washing solution so that it was in a concentration of 0.12 % . Mixture B was added to another identical wash solution to make the concentration thereof 0.12 % . Originally, each of the wash solutions containing the detergent mixture had a pH of 10.0. A 10 minute wash cycle was used with each wash solution. After about 1 minute, the coatings surrounding the enzyme and sulfamic acid of mixture B dissolved. Simultaneously with the release of the sulfamic acid into the washing solution, the pH of the washing solution changed to a value of about 7.0. After 10 minutes, the three strips were removed from each solution, graded using a Hunter Color and Color Difference Meter, and the mean determined. The above procedure was repeated for each row of strips containing the various _/ aforementioned spots.,

The results of the tests, expressed in terms of relative Hunter-White units are as follows. The greater the value is, the greater the amount of stains removed.

Spinach liqueur beef liver sauce

4th , 48 4, 46 9 .23 3 , 83 12th , 37 9, 43 20th , 90 20th , 90

Mixture A Mixture B

least significant

Deviation 3.20 1.64 2.51 2.02

309844/10 5 4

The above results show that with the mixture according to the invention, i.e. with the mixture B, significantly better stain removal is achieved, than with a mixture of the prior art, i.e. with mixture A.

When the above tests were repeated except that the enzyme of Mixture B was replaced with an enveloped alkaline protease, acidic protease, or amylase, and an enveloped pH control agent was used in an amount sufficient to maintain the pH change the washing solution to a pH at which the corresponding enzyme works best _? essentially comparable results were obtained.

Example 2

Sodium tripolyphosphate 35 % Sodium alkyl sulfate (with 12 carbon atoms) 30 # Sodium sulfate 20 I Alealase, coated with tallow fatty acid 5% Phosphoric acid, coated with tallow fatty acid 1% Res1> (water) 9%

About 2 minutes after the above mixture was added to the water, the phosphoric acid was released, the pH of the solution being changed to about 9 _sec . Immediately thereafter, the alealase was released.

309844/1054

Example 3

Sodium tripolyphosphate
Sodium salt of sulfated Cg
ethoxylated with 5 mol of ethylene oxide "20 % sodium silicate (SiO ₃ : Na ₂ O = 2.0) 20 %

Sodium sulfate 10 %

Alkaline protease with optimal proteolytic activity at pH 10.5> coated with coconut fatty alcohol 0.001 %

Sodium hydroxide, coated with a polyethylene glycol with a molecular weight of 6,000 0.5 %

Rest (water) k _t

When the above mixture was added to the water, it gave the water a pH of about 10.0. About 1 minute later the sodium hydroxide was released. After this release, the pH of the solution was about 10.5 * therefore the enzyme was released simultaneously with the sodium hydroxide to hit · _e s to a pH value of the solution, which worked best.

The stain removal properties of the mixtures illustrated in Examples 2 and 3 were very satisfactory.

example ¹ y

An example of a pre-soak type detergent product that is added to a wash solution about 60 minutes after it is added the pH of the same was adjusted to a value of 9> 0 and the enzyme was released

309844/1054

the following composition:

Sodium tripolyphosphate JO%

Sodium perborate 25 %

Alcalase, coated with mineral oil 1.5 %

Sulphamic acid, coated with mineral oil l ', 5 %

Rest (water) 2%

The cleaning and whitening benefits of soiled fabrics, which were soaked in a solution containing the above mixture were excellent.

Example 5

It was a detergent mixture that had the same components as contained in Example 2, formulated. The alcalase and the phosphoric acid, however, formed a (discreet) unit with a coating of sebum fatty acid. About 2 minutes after it was added to a washing solution, the coating became dissolved, whereby the alcalase and the acid were released at the same time. This made sure that the enzyme released at the desired pH, i.e. at about 9> O became.

3Q9844 / 105

Claims (12)

Patent claims: ) Enzyme Detergenzgemisch containing suitable to achieve _s in an aqueous solution successively different pH values, characterized in that substantially it out. a) a water-soluble anionic, non-ionic, amphateric or zwitterionic detergent or mixtures the same, b) from about ₁ O OOl% to 10% of an enzyme which is coated with a normally solid water-soluble or wasserdxspergierbaren material which the release of the enzyme in the aqueous solution of 0.5 minutes to hours after the k Detergenzgemisch the solution was added , permitted and c) a pH regulating agent in an amount, which is sufficient to raise the pH of the aqueous solution ti <- / to set ■ ■ ". ,. . The maximum value / at which the enzyme is most effective encased in a normally solid water-soluble or water-dispersible material so that the pH regulating agent is released into the solution immediately prior to or simultaneously with the release of the enzyme ₉ . 2.) enzyme-containing detergent mixture according to claim 1, characterized in that the enzyme is released into the aqueous solution from 0 _s 5 minutes to 5 minutes after the detergent mixture has been added to the water / water. 309844/1054 3 ·) enzyme-containing detergent mixture ,, according to claim 1, characterized in that the enzyme is in the aqueous solution from 30 minutes to 4 hours after the detergent mixture to which water was added, is released. 4.) enzyme-containing detergent mixture according to claim 2, characterized in that the enzyme is coated with a polymer of ethylene glycol. 5.) enzyme-containing detergent mixture according to claim 2, characterized in that the pH regulating agent comprises a fatty acid having 12 to 18 carbon atoms is wrapped. ". = -.- - 6.) enzyme-containing detergent mixture according to claim 2, characterized in that the enzyme is a proteolytic Enzyme and that the pH regulating agent is in an amount sufficient to maintain the pH to change from 7 to 9. 7.) enzyme-containing detergent mixture according to claim 2, characterized in that it additionally contains a water-soluble alkaline builder, the ratio of detergent: builder from 10: 1 to 1:10. 8.) enzyme-containing detergent mixture according to claim 2, characterized in that the enzyme is an acidic protease and that the pH regulating agent in one Amount is present that is sufficient to raise the pH can be changed from 3.0 to 7 * 0. 309644/1054 231B930 9) enzyme-containing detergent mixture according to claim 8, characterized in that it further comprises a second pH-regulating agent, which with a water-soluble or water-dispersible material is encased, in an amount sufficient to bring the pH to 7.0 to change to 9.0 and contains a bleach that has a water-soluble or water-dispersible material is enveloped so that the bleach simultaneously with or immediately after the release of the second pH regulating agent is released into the wash solution. 10.) enzyme-containing detergent mixture according to claim 1, characterized in that the enzyme and the pH regulating agents form a (discreet) unit. 11.) enzyme-containing detergent mixture according to claim 10, characterized in that the enzyme forms a core, the successive a water-soluble or water-dispersible coating, a coating of one of the pH regulating agents and a second water-soluble or water-dispersible coating. 12.) Enzyme-containing detergent mixture which is suitable, in the case of an aqueous solution, successively different To achieve pH values, characterized in that it consists essentially of a) a water-soluble alkaline builder, b) an anionic, non-ionic, amphoteric or zwitterionic detergent or mixtures thereof, wherein the ratio of detergent: builder is from 10: 1 to 1:10, 3Q9844 / 1054 c) from 0.05 % to 5 % of a proteolytic enzyme which exhibits optimum stain removal performance at a pH of 7 to 9 and is coated with a sufficient amount of a water soluble or dispersible material which contains the enzyme concurrently with or ■ immediately after the "release of the pH regulating agent according to (d) releases, and d) a sufficient amount of a pH regulating agent to adjust the pH of the washing solution to from 7 to 9, which is coated with a water-soluble or water-dispersible coating, the enveloping material releasing the pH-regulating agent _{By means of delayed y} from 0.5 minutes to 5 minutes after the detergent mixture was first added to the wash solution. 13 ·) Method of washing fabrics with an enzyme containing detergent mixture according to claim 12, characterized characterized in that it comprises the following stages: a) move the water with the enzyme-containing detergent. mixture according to claim 12, b) the detergent and builder act for up to 5 minutes at pH 9.5 to 10.5 on the tissue, c) after 0.5 to 5 minutes, release of the pH-regulating agent By means of which the pH of the washing solution is changed from 7 to 9, and 309844/105 d) Release of the proteolytic enzyme at the same time or immediately after the release of the pH regulating agent. For: The Procter & Gamble Company Cincinnati, Ohio, V.St.A. (Dr.H. ^ hr.Beil) Lawyer 309844/1054